Abstract
Complex phosphates Ca0.5 + x Zn x E2 − x (PO4)3 (E = Ti, Zr) having NaZr2(PO4)3 (NZP) structure have been prepared and characterized by X-ray diffraction, electron probe microanalysis, IR spectroscopy, and differential thermal analysis (DTA). Their phase formation has been studied by X-ray powder diffraction and DTA. The concentration and temperature fields of existence of these NZP phases have been determined: substitution solid solutions exist in the range of compositions where 0 ≤ x ≤ 0.5. The Ca0.7Zn0.2Ti1.8(PO4)3 crystal structure has been refined by the Rietveld method (space group \(R\bar 3\), a = 8.3636(4) A, c = 21.9831(8) A, V = 1331.7(1) A3, Z = 6). The framework in the NZP structure is built of octahedra, which are populated by titanium and zinc atoms, and PO4 tetrahedra. Calcium atoms occupy extraframework positions. Extensive solid solution formation due to the accommodation of cations(2+) in the interstices within the NZP framework (M) and in the framework-forming octahedra (M′) makes it possible to design a plurality of new M0.5 + x M′ x E2 − x (PO4)3 phosphates with tailored structures.
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